Polyphosphites



United States Patent M 3,375,304 POLYPHOSPHITES Millard S. Larrison, Livingston, N.J., assignor, by mesne assignments, to Small Business Administration, Richmond, Va., and First National Bank of Morgantown,

Morgantown, W. Va.

No Drawing. Filed Jan. 4, 1965, Ser. No. 423,393

9 Claims. (Cl. 260-929) ABSTRACT OF THE DISCLOSURE Compounds are prepared having the formula R10 0R6 \POR3O/POR5O\ The present invention relates to novel polymeric phosphites.

' It is an object of the present invention to prepare improved sta bilizers for natural and synthetic rubber.

Another object is to prepare novel stabilizers for vinyl chloride polymers.

A further object is to prepare novel phosphites having at least three phosphorus atoms in the molecule.

An additional object is to prepare phosphites of improved hydrolytic stability.

Still further objects and the entire scope of applicability of the present invention will become apparent from the detailed description given hereinafter; it should be understood, however, that the detailed description and specific examples, while indicating preferred embodiments of the invention, are given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description.

It has now been found that these objects can be attained by preparing phosphites having the formula hydrolytic stability is obtained than when R R R R and R are phenyl or alkylphenyl having up to 3 carbon atoms in the alkyl group. Most preferably R R R R and R lare alkylphenyl having at least eight carbon atoms in the alkyl-group in ,order to get maximum hydrolytic stability. It will be understood that positional isomers exist for the compounds having or more phosphorus atoms.

Preferably R and R are residues of polypropylene glycol since better hydrolytic stability is obtained due Patented Mar. 26, 1968 to the presence of linkages to the phosphorus atoms which are residues of secondary alcohols. (The normal method for preparing polypropylene glycols results in over of secondary alcohol groups.) Most preferably R and R are residues of polypropylene glycols having 6-8 repeating units such as polypropylene glycol 425 (polypropylene glycol with a molecular weight of 425). Other polyalkylene glycol residues within R and R include polyethylene glycol, polytetramethylene glycol, poly butylene glycol and polytrimethylene glycol. Mixtures of polyalkylene glycols or mixtures of these with alkylidene bisphenol or hydrogenated alkylidene bisphenols are also within the scope .of R and R In Formula I n is an integer of at least 1 and can be 20 or more.

Compounds within the present invention include pentakis (nonylphenyl) bis (polypropylene glycol 425) triphosphite, hexakis (nonyl phenyl) tris (polypropylene glycol) tetraphosphite, heptakis (nonyl phenyl) tetrakis (polypropylene glycol 425 pentaphosphite, octakis (nonyl phenyl) pentakis (polypropylene glycol 425) hexaphosphite, nonakis (nonyl phenyl) hexakis (polypropylene glycol 425 heptaphosphite, decakis (nonyl phenyl) heptakis (polypropylene glycol 425 octaphosphite, eicosakis (nonyl phenyl) heptadecakis (polypropylene glycol 425) octadecaphosphite, docosakis (nonyl phenyl) nonadecakis (polypropylene glycol 425) eicosaphosphite, pentakis (octylphenyl) bis (polypropylene glycol'425) triphosphite, hexakis (octylphenyl) tris (polypropylene glycol 425) tetraphosphite, heptakis (octylphenyl) tetrakis (polypropylene glycol 425 pentaphosphite, octakis (octylphenyl) pentakis (polypropylene glycol 425 hexaphosphite, decakis (octylphenyl) heptakis (polypropylene glycol 425) octaphosphite, pentakis (butylphenyl) bis (polypropylene glycol 425 triphosphite, heptakis (butylphenyl) tetrakis (polypropylene glycol 425) pentaphosphite, decakis (butylphenyl) heptakis (polypropylene glycol 425 octaphosphite, pentakis (dodecylph'enyl) bis (polypropylene glycol 425) triphosphite, heptakis (d0- decylphenyl) tetrakis (polypropylene glycol 425) pentaphosphite, pentakis (octadecylphenyl) bis (polypropylene glycol 425) triphosphite, octakis (octadecylphenyl) pentakis (polypropylene glycol 425 hexaphosphite, pentakis (phenyl) bis (polypropylene glycol 425) triphosphite, heptakis (phenyl) tetrakis (polypropylene glycol 425) pentaphosphite, undecakis (phenyl) octakis (polypropylene glycol 425) nonaphosphite, pentakis (methylphenyl) bis (polypropylene glycol 425 triphosphite, octakis (methylphenyl) pentakis (polypropylene glycol 425 hexaphosphite, hexakis (propylphenyl) tris (poly propylene glycol 425) tetraphosphite, pentakis (nonylphenyl) bis (dipropylene glycol) triphosphite, hexakis (octylphenyl) tris (dipropylene glycol) tetraphosphite, heptakis (decylphenyl) tetrakis (dipropylene glycol) pentaphosphite, decakis (nonylphenyl) heptakis (dipropylene glycol) octaphosphite, heptakis (octylphenyl) tetrakis (tripropylene glycol) pentaphosphite, pentakis (nonylphenyl) bis (polypropylene glycol molecular weight 365) triphosphite, heptakis (nonylphenyl) tetrakis (polypropylene glycol molecular weight 485) pentaphosphite, octakis (octylphenyl) pentakis (polypropylene glycol molecular weight 2025) phosphite, pentakis (nonylphenyl) bis (polypropylene glycol molecular weight 2025) triphosphite, pentakis (amylphenyl) bis (polyethylene glycol molecular weight 2000) triphosphite, pentakis (2,4,6-trichlorophenyl) bis (polypropylene glycol 425) triphosphite, heptakis (nonylphenyl) tetrakis (polyethylene glycol molecular weight 310) pentaphosphite, nonakis (hex- .ylphenyl) hexakis (diethylene glycol) heptaphosphite, heptakis (pentachlorophenyl) tetrakis (polypropylene glycol 425 pentaphosphite, heptakis (nonylphenyl) tetrakis (polytetramethylene glycol molecular weight 450) pentaphosphite, pentakis ('heptylphenyl) bis (polytrimethylene glycol molecular weight 425) triphosphite, heptakis (octylphenyl) tetrakis (poly-1,2-butylene glycol molecular weight 500) pentaphosphite, pentakis (nonylphenyl) bis (bisphenol A) triphosphite, heptakis (nonylphenyl) tetrakis (bisphenol A) pentaphosphite, nonakis (octylphenyl) hexakis (bisphenol A) heptaphosphite, pentakis (nonylphenyl) bis (4,4-isopropylidene dicyclohexanol) triphosphite, heptakis (octylphenyl) tetrakis (4,4 isopropylidene dicyclohexanol) pentaphosphite, hexakis (octylphenyl) tris (tetrabromobisphenol A) tetraphosphite, pentakis (nonylphenyl) bis (tetrachlorobisphenol A) triphosphite, heptakis (nonylphenyl) tetrakis (tetrachlorobisphenol A) pentaphosphite, heptakis (nonylphenyl) bis (polypropylene glycol-4,4-isopropylidene dicyclohexanol) tetraphosphite, octakis (nonylphenyl) bis (polypropylene glycol 425) tris (dipropylene glycol) hexaphosphite, hexakis (pentabromophenyl) tris (polypropylene glycol 425) tetraphosphite, heptakis (nonylphenyl) bis (polypropylene glycol 425) bis (polyethylene glycol 400 molecular weight) pentaphosphite, heptakis (4-chlorophenyl) tetrakis (polypropylene glycol 425) pentaphosphite.

Unless otherwise indicated in the specification the alkylphenyl has the alkyl group in the para position. Thus in the preceding paragraph the alkyl groups are in the position para to the oxygen substituent on the phenyl. However, the invention is equally applicable to the meta and ortho alkylphenyl compounds and the claims include all three isomers. Thus, for example, there are included within the invention pentakis (o-nonylphenyl) bis (polypropylene glycol 425) triphosphite, heptakis (m-nonylphenyl) tetrakis (polypropylene glycol 425) pentaphosphite, and octakis (o-octylphenyl) pentakis (dipropylene glycol) hexaphosphite, heptakis (p-tert.-octylphenyl) tetrakis (polypropylene glycol 425) pentaphosphite.

Unless otherwise indicated all parts and percentages are by weight.

The products of the present invention can be incorporated in an amount of 0.01 to into halogen containing vinyl and vinylidene resins. Preferably, the resin is a vinyl halide resin, specifically, a vinyl chloride resin. Usually, the vinyl chloride resin is made from monomers consisting of vinyl chloride alone or a mixture of monomers comprising at least vinyl chloride by weight. When vinyl chloride copolymers are stabilized, preferably the copolymer of vinyl chloride with an ethylenically unsaturated compound copolymerizable therewith contains at least 10% of polymerized vinyl chloride.

As the chlorinated resin there can be employed chlorinated polyethylene having 14 to e.g. 27% chlorine by weight, polyvinyl chloride, polyvinylidene chloride, polyvinyl bromide, polyvinyl fluoride, copolymers of vinyl chloride with l to preferably 1 to 30%, of a copolymerizable ethylenically unsaturated material such as vinyl acetate, vinyl butyrate, vinyl benzoate, vinylidene chloride, diethyl fumarate, diethyl maleate, other alkyl fumarates and maleates, vinyl propionate, methyl acrylate, 2-ethylhexyl acrylate, butyl acrylate and other alkyl acrylates, methyl methacrylate, ethyl methacrylate, butyl methacrylate, and other alkyl methacrylates, methyl alpha chloroacrylate, styrene, trichloroethylene, vinyl ethers such as vinyl ethyl ether, vinyl chloroethyl ether and vinyl phenyl ether, vinyl ketones such as Vinyl methyl ketone and vinyl phenyl ketone, l-fluoro-l-chloroethylene, acrylonitrile, chloroacrylonitrile, allylidene diacetate and ch10- roallylidene diacetate. Typical copolymers include vinyl chloride-vinyl acetate (96:4 sold commercially as VYNW), vinyl chloride-vinylacetate (87:13), vinyl chloride-vinyl acetate-maleic anhydride (86: 13 1), vinyl chloride-vinylidene chloride (:5 vinyl chloride-diethyl fumarate (95:5), vinyl chloride-trichloroethylene (95:5), vinyl chloride-Z-ethylhexyl acrylate (80:20).

In addition to imparting heat stability to vinyl chloride resins it has been found that they also improve the clarity of such resins. Thus the addition of 1% of heptakis (nonylphenyl) tetrakis (polypropylene glycol 425) pentaphosphite to polyvinyl chloride gives a stabilized product of excellent clarity.

Of course there can also be added group II metal salts to the vinyl chloride formulations in an amount of 0.1- 10% as is conventional in the art. Such salts include barium-cadmium laurate, zinc stearate, calcium 2-ethylhexoate, barium nonylphenolate, barium octylphenolate, zinc octoate and barium stearate.

The products also are excellent stabilizers for hydrocarbon polymers when used in an amount of 0.01 to 20% of the polymer. Thus they can be employed to stabilize polyethylene, polypropylene, ethylenepropylene copolymer (eg a 50:50 copolymer), polystyrene, acrylonitrilebutadiene-styrene terpolymer, natural rubber, GR-S (rubbery butadiene-styrene copolymer), cis isoprene polymer, polybutadiene, polyisobutylene, isobutylene-butadiene copolymer (e.g. butyl rubber such as a 97:3 copolymer). They can also be used to improve the fire resistance of cellulose, cellulose esters and ethers, e.g. cellulose acetate, cellulose nitrate, cellulose acetate-butyrate, ethyl cellulose, polystyrene, polyethylene, polypropylene and other polymeric monoolefins and polyolefins.

The compounds can be prepared in several ways. Thus there can be employed reactants according to Equation 1, 2, 3 or 4 infra.

where R is alkyl, and R and n are as previously defined.

where n, R and R are as previously defined.

RFGO P (n+1)HOR5OH n (n+4)OH nRtGOH where n, R and R are as previously defined. Example 2 where R R and n are as previously defined.

The reaction under all of Equations 1-4 is preferably catalyzed with 0.1-5 by weight of the starting phosphite reactant of a dialkyl phosphite, a diaryl phosphite, a dihaloaryl phosphite or an alkaline catalyst such as an alkali metal alcoholate or phenolate. As examples of catalysts there can be used diphenyl phosphite, didecyl phosphite, phenyl decyl phosphite, di(o-cresyl) phosphite, di(p-cresyl) phosphite, di(m-cresyl) phosphite, di(monylphenyl) phosphite, di(p-dodecylphenyl) phosphite, di(ochlorophenyl) phosphite, di(2,4-dimethy1phenyl) phosphite, di(p-bromphenyl) phosphite, diethyl phosphite, dicyclohexyl phosphite, dioctadecyl phosphite, sodium phenolate, sodium decylate, potassium phenolate, potassium cresylate, sodium ethylate and sodium octadecanolate. Diaryl phosphites are the preferred catalysts.

1182 grams (1 mole) of tetrakis (nonylphenyl) hydrogenated bisphenol A diphosphite (prepared according to application Serial No. 366,891, filed May 12, 1964),.850

C nHre Example 1 860 grams (1.25 moles) of tris(nonylphenyl) phos phite, 310 grams (1.00 mole) of triphenyl phosphite, 637 grams (1.50 moles) of polypropylene glycol 425 and 10 grams of diphenyl phosphite as a catalyst were heated and the phenol removed by vacuum distillation. Terminal conditions were 195 C. and 2 mm. There was removed 289 grams of distillate (almost all phenol) with a set point of 38 C. At the end of the distillation period the flask contents were medium red in color. The product was treated at 150 C. with 10 grams of soda ash, 10 grams of filter aid (Hi-Flow) and 10 grams of attapulgus clay (Attagel). On addition to the soda ash the product immediately changed from red to light yellow. After stirring 10 minutes at 140150 C. the product was filtered through Whatman No. 3 filter paper. The product was pentakis (nonylphenyl) bis polypropylene glycol 425) triphosphite, a clear, light yellow viscous fluid R.I. at 25 C. 1.5006, acid number 0.03, sp. gr. at 25 C. 1.04, and phosphorus content 4.54.6%, molecular weight 2034.

grams (2 moles) of polypropylene glycol 425, 457 grams mole) of tris (nonylphenyl) phosphite, 547 grams moles) of triphenyl phosphite and 10 grams of diphenyl phosphite (catalyst) were heated and the phenol formed removed at reduced pressure. Terminal conditions were 170 C. and 2 mm. 404 grams of distillate were recovered (mainly phenol) with a set point of 34 C.

At the end of the distillation the product in the flask had a deep red color. It was cooled to 150 C. and treated with 20 grams of soda ash and filtered. The product became light yellow in color upon contact with the soda ash. The product was hexakis (nonylphenyl) bis (polypropylene glycol) hydrogenated bisphenol A tetraphosphite having a R.I. at 25 C. of 1.5104, acid number of 0.013 and specific gravity at 25 C. of 1.04 and phosphorus content 4.9%, molecular weight 2524. The product was a mixture of with isomeric compounds containing the polypropylene glycol and hydrogenated disphenol A linking groups.

Example 3 802 grams (1 /6 moles) of tris (nonylphenyl) phosphite, 850 grams (2 moles) of polypropylene glycol 425, 413 grams (1 /3 moles) of triphenyl phosphite and 10 grams of diphenyl phosphite (catalyst) were heated and the phenol removed at 2-5 mm. pressure. Terminal conditions were 195' C. and 2 mm. There were removed 37 grams of phenol distillate, set point 38 C.

The residue was treated with sodium carbonate, Attagel and Hi-Flow and filtered. The product was a pale yellow fluid of medium viscosity, R.I. at 25 C. 1.4959, acid number 0.02; it was heptakis (nonylphenyl) tetrakis (polypropylene glycol 425) pentaphosphite, molecular weight 3380, phosphorus content 4.59%.

It was a mixture of isomeric materials having the formulae 0 CnHn CoHw CnHn Ca io and PPG425 Uv io P C 9 19 O CnH The procedure of Example 3 has been repeated on numerous occasions and the product is now available commercially as Weston 1700 phosphite with the following properties, refractive index N 1.49501.4970; specific gravity 25 C./25 C. 1.0121.022, acid number mg. KOH/gm. maximum 0.5, phosphorus 4.54.6%, insoluble in water but miscible with benzene, toluene and n hexane.

The product of Example 3 showed remarkable hydrolytic stability for a phosphite. Thus on stirring the heptakis (nonylphenyl) tetrakis (polypropylene glycol 425) pentaphosphite with distilled water at 25 C The mixture developed a pH of 6. Contact with the water was maintained for 48 hours at 2025 C. The pH did not undergo change during this period, indicating remarkable hydrolytic stability. At the end of this period, the mixture of water and the polyphosphite still reduced silver nitrate solution rapidly.

Example 4 1146 grams (1 /3 moles) of tris (nonylphenyl) phosphite, 1487 grams (3 /2 moles) of polypropylene glycol 425, 723 grams (2 /3 moles) of triphenyl phosphite and 15 grams of diphenyl phosphite were heated and 660 grams of phenol formed removed by vacuum distillation in the manner described in Example 3. The residue in the flask was treated with sodium carbonate and filtered to recover decakis (nonylphenyl) heptakis (polypropylene glycol 425) octaphosphite, molecular weight 5400, P 4.59%, R.I. 1.4930, acid number 0.05, sp. gr. 1.00 as a light yellow oil of medium viscosity.

In the above series of polyphosphites. the viscosity increases very slowly. The viscosity of the polyphosphite member having 8 phosphorus atoms is only 75% greater than that of the monomeric compound having 2 phosphorus atoms.

Example 5 There was charged into a 5 liter flask equipped with stirrer, vacuum seal, heater and distillation take off for vacuum operation802 grams (1% moles) of tris (nonylphenyl) phosphite, 456 grams (2 moles) of bisphenol A, 413 grams (1% moles) of triphenyl phosphite and grams of diphenyl phosphite. There was stripped out 360 grams of phenol under vacuum (theory 376 grams). Terminal conditions were 184 C. and 29.5 inch vacuum. Theresidue in the flask was stirred with 8 grams of soda ash and 10 grams of Hi-Flow. filter aid and filtered at 155 C.

The heptakis (nonylphenyl) tetrakis (bisphenol A). pentaphosphite thus produced was a very viscous, light yellow oil, molecular weight 2592, P 5.78%.

Example 6 The procedure of example 3 was repeated replacing the polypropylene glycol 425 by 2 moles of dipropylene glycol to produce heptakis (nonylphenyl) tetrakis (dipropylene glycol) pentaphosphite.

Example 7 The procedure of Example 3 was repeated replacing CoHm the polypropylene glycol 425 by 2 moles of triethylene glycol and replacing the tris (nonylphenyl) phosphite by 1% moles of tris (octylphenyl) phosphite to produce heptakis (octylphenyl) tetrakis (triethylene glycol pentaphosphite.

Example 8 1 part of heptakis (nonylphenyl) tetrakis (polypropylene glycol 425) pentaphosphite was mixed with parts of vinyl chloride resin (Goodrich 103 Ep) to give a stabilized composition.

Example 9 2 parts of heptakis (nonylphenyl) tetrakis (polypropylene glycol 425) pentaphosphite was mixed with 100 parts of solid polypropylene (melt index 0.8) to give a stabilized product.

Example 10 1 part of heptakis (nonylphenyl) tetrakis (polypropylene glycol 425) pentaphosphite and 2 parts of bariumcadmium laurate were mixed with 100 parts of polyvinyl chloride and 50 parts of dioctyl phthalate to give a stabilized product.

Example 11 The procedure of Example 3 was repeated replacing the polypropylene glycol 425 by 2 moles of tetrachloro bisphenol A to produce heptakis (nonylphenyl) tetrakis (tetrachloro bisphenol A) pentaphosphite.

Example 13 There was charged into a flask 1,290 grams (3 moles) of tris (dipropylene glycol) phosphite, 517 grams (1% moles) of triphenylphosphite, 2,293 grams, (3 /3 moles) of tris (nonylphenyl) phosphite and 20 grams of diphenyl phosphite. The distillate stripped out under vacuum totaled 76 8 grams and consisted of 275 grams of dipropylene glycol, 485 grams of phenol and 8 grams of nonylphenol, terminal distillation conditions were 192 C. and 6 torr. Theoretical yields of distillate from pure starting materials are 470 grams of phenol (5 moles) and 268 grams of dipropylene glycol (2 moles).

At the end of the distillation period, the residue was allowed to cool to 150 C. and 20 grams of dry sodium carbonate added to neutralize the acid and destroy the catalyst. The color changed rapidly from a medium red to a very light yellow on addition of the carbonate. After about 15 minutes of stirring the mixture was subjected to vacuum filtration at l50 C.

The decakis (nonylphenyl) heptakis (dipropylene glycol) octaphosphite product obtained was a clear, light yellow fluid of medium viscosity having an R.I. at 25 C. of 1.5130, acid No. 0.0. Fluid had good resistance to hydrolysis but was hydrolyzed somewhat more rapidly than the analogous compound using polypropylene glycol 425.

Example 14 The same product as that obtained in Example 13 was obtained by using 1,003 grams (2 /3 moles) of tris (dipropylene glycol)phosphite, 723 grams (2 /3 moles) of triphenyl phosphite, 2,293 grams (3 /3 moles) of tris (nonylphenyl) phosphite and 20 grams of diphenyl phosphite and stripping out 658 grams (7 moles) of phenol.

What is claimed is:

where R R R R and R are selected from the group consisting of phenyl, alkyl phenyl having 1 to 18 carbon atoms in the alkyl group, chlorophenyl and bromophenyl, R and R are a member of the group consisting of polyalkylene glycol, and hydrogenated alkylidene bisphenol, and n is an integer of 1 to 18.

2. Penta to docosakis (phenyl or alkyl phenyl having 1 to 18 carbon atoms in the alkyl group) di to nonadeca (poly lower alkylene glycol) tris to eicosakis phosphite, there being 3 less polyalkylene glycol groups and 2 less phosphorous atoms than aryl groups.

ORB

3. Penta to docosakis (phenyl or alkyl phenyl having 1 to 18 carbon atoms in the alkyl group) his to nonadecakis (polypropylene glycol) tris to eicosakis phosphite, there being 3 less polypropylene glycol groups and 2 less phosphorous atoms than aryl groups.

4. Penta to docosakia (alkylphenyl) bis to nonadecakis (polypropylene glycol) tris to eicosakis phosphite, there being 3 less polypropylene glycol groups and 2 less phosphorus atoms than alkylphenyl groups, said alkyl having 4 to 18 carbon atoms.

5. A compound according to claim 4 wherein said polypropylene glycol group has 6 to 8 oxypropylene units.

6. Pentakis (nonylphenyl) bis (polypropylene glycol 425) triphosphite.

7. Heptakis (nonylphenyl) glycol 425 pentaphosphite.

8. Penta to decakis (alkylphenyl) bis to heptakis (polypropylene glycol) tris to octakis phosphite, there being 3 less polypropylene glycol groups and 2 less phosphorus atoms than alkylphenyl groups, said alkyl having 7 to 12 carbon atoms.

9. Penta to decakis (alkylphenyl) his to heptakis (polyethylene glycol) tris to octakis phosphite, there being 3 less polyethylene glycol groups and 2 less phosphorus atoms than alkyl phenyl groups, said alkyl having 7 to 12 carbon atoms, said polyethylene glycol having at least 3 oxyethylene units.

References Cited UNITED STATES PATENTS 9/ 1952 Nelson 26'0 -930 XR tetrakis (polypropylene CHARLES B. PARKER, Primary Examiner.

A. H. SUTTO, Assistant Examiner. 

